Aminophenols useful as intermediates for formazan reactive dyes

ABSTRACT

There are described formazan dyes of the formula ##STR1## where m and n are each 1 or 2, 
     Kat.sup.⊕ is the equivalent of a cation, 
     Me is copper or nickel, 
     X is oxygen or a radical of the formula CO--O or SO 2  --0, 
     Y is vinyl or a radical of the formula C 2  H 4  --Q, wherein Q is a group that is detachable under alkaline reaction conditions, 
     E is a fiber-reactive radical, 
     the rings A and B may be substituted and benzofused, and 
     the ring C may be substituted, 
     the use thereof for dyeing or printing hydroxyl- or nitrogen-containing organic substrates, novel aminophenols and a process for preparing same.

This is continuation, of application Ser. No. 08/136,131 filed on Oct.15, 1993, now U.S. Pat. No. 5,446,193.

The present invention relates to novel formazan dyes of the formula I##STR2## where m and n are each independently of one another 1 or 2,

Kat.sup.⊕ is the equivalent of a cation,

Me is copper or nickel,

X is oxygen or a radical of the formula CO--O or SO₂ --O,

Y is vinyl or a radical of the formula C₂ H₄ --Q, wherein Q is a groupthat is detachable under alkaline reaction conditions,

E is a heterocyclic fiber-reactive radical or a fiber-reactive radicalof the formula L--W, wherein L is a bridge member and W is afiber-reactive radical of the aliphatic series,

the rings A and B are each substituted or unsubstituted and may bebenzofused, and

the ring C is substituted or unsubstituted,

the use thereof for dyeing or printing hydroxyl- or nitrogen-containingorganic substrates, novel aminophenols, and a process for preparingthem.

Metal complex formazan dyes with reactive groups are known per se; seefor example EP-A-28 788. However, the prior art dyes frequently havedefects in their application properties.

It is an object of the present invention to provide novel formazan-basedreactive dyes which shall be notable for an advantageous applicationproperty profile.

We have found that this object is achieved by the formazan dyes of theformula I defined at the beginning.

Attention must be drawn in particular to formazan dyes of the formula Ia##STR3## where Z¹ is hydrogen or hydroxysulfonyl,

Z² is hydrogen, C₁ -C₄ -alkanoylamino, halogen or nitro,

Z³ and Z⁴ are each independently of one another hydrogen, halogen, C₁-C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylsulfonyl, nitro orhydroxysulfonyl,

Z⁵ and Z⁶ are each independently of one another hydrogen,hydroxysulfonyl, halogen, nitro, carboxyl, ureido, substituted orunsubstituted mono- or di(C₁ -C₄ -alkyl)ureido, substituted orunsubstituted phenylureido, substituted or unsubstituted phenyl,substituted or unsubstituted C₁ -C₄ -alkanoylamino, substituted orunsubstituted benzoylamino, C₁ -C₄ -alkoxycarbonylamino, substituted orunsubstituted mono- or dialkylcarbamoyl or substituted or unsubstitutedmono-or dialkylsulfamoyl,

the rings D and G may each be benzofused, and m, n, Kat.sup.⊕, Me, E, Xand Y are each as defined above.

Any alkyl appearing in the abovementioned formulae may be straight-chainor branched.

Any substituted alkyl appearing in the abovementioned formulae may haveas substituents for example, unless otherwise stated, hydroxysulfonyl,carboxyl, hydroxyl or sulfato. The number of substituents in substitutedalkyl is in general 1 or 2.

Any substituted phenyl appearing in the abovementioned formulae may haveas substituents for example, unless otherwise stated, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, halogen, nitro, C₁ -C₄ -alkanoyl, C₁ -C₄ -alkanoylamino,benzoylamino or hydroxysulfonyl. The number of substituents insubstituted phenyl is in general from 1 to 3.

Kat.sup.⊕ is the equivalent of a cation. It constitutes either a protonor is derived from metal or ammonium ions. Metal ions are in particularlithium, sodium and potassium ions. Ammonium ions for the purposes ofthe present invention are substituted or unsubstituted ammonium cations.Substituted ammonium cations are for example monoalkyl-, dialkyl-,trialkyl-, tetralkyl- or benzyltrialkyl-ammonium cations or cationsderived from nitrogen-containing five- or six-membered saturatedheterocycles, such as pyrrolidinium, piperidinium, morpholinium,piperaziniumor N-alkylpiperaziniumcations or their N-monoalkyl- orN,N-dialkyl-substituted products. Alkyl used herein in the general senseof meaning straight-chain or branched C₁ -C₂₀ -alkyl which may besubstituted by hydroxyl and/or interrupted by oxygen atoms in etherfunction.

Particularly notable cations are protons and lithium, sodium andpotassium ions.

Q is a group that is detachable under alkaline reaction conditions.Examples of groups of that kind are chlorine, bromine, C₁ -C₄-alkylsulfonyl, phenylsulfonyl, OSO₃ H, SSO₃ H, OP(O)(OH)₂, C₁ -C₄-alkylsulfonyloxy, substituted or unsubstituted phenylsulfonyloxy, C₁-C₄ -alkanoyloxy, C₁ -C₄ -dialkylamino and a radical of the formula##STR4## where R¹, R² and R³ are identical or different and each isindependently of the others C₁ -C₄ -alkyl or benzyl and is in each casethe equivalent of an anion. Suitable anions are for example fluoride,chloride, bromide, iodide, mono-, di- or trichloroacetate,methanesulfonate, benzenesulfonate and 2- or 4-methylbenzenesulfonate.

Z², Z³, Z⁴, Z⁵ and Z⁶ are each for example fluorine, chlorine orbromine.

Z⁵ and Z⁶ may each also be for example N-methylureido, N-ethylureido,N-propylureido, N-isopropylureido, N-butylureido,N-(2-hydroxysulfonylethyl)ureido, N-(2-sulfatoethyl)ureido,N,N-dimethylureido, N-methyl-N-(2-sulfatoethyl)ureido, phenylureido,phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or4-chlorophenyl, 2-, 3- or 4-hydroxysulfonylphenyl, formylamino,acetylamino, propionylamino, butyrylamino, isobutyrylamino,3-hydroxysulfonylpropionylamino, 3-carboxypropionylamino, benzoylamino,2-, 3- or 4-hydroxysulfonylbenzoylamino, 2-, 3- or 4-chlorobenzoylamino,2-, 3- or 4-methylbenzoylamino, 2-, 3- or 4-carboxylbenzoylamino,methoxycarbonylamino, ethoxycarbonylamino, propoxycarbonylamino,isopropoxycarbonylamino, butoxycarbonylamino, carbamoyl, mono- ordimethylcarbamoyl, mono- or diethylcarbamoyl, mono- ordipropylcarbamoyl, mono- or diisopropylcarbamoyl, mono- ordibutylcarbamoyl, N-methyl-Nethylcarbamoyl,N-methyl-N-(2-hydroxysulfonylethyl)carbamoyl, sulfamoyl, mono- ordimethylsulfamoyl, monoor diethylsulfamoyl, mono- or dipropylsulfamoyl,mono- or diisopropylsulfamoyl, mono- or dibutylsulfamoyl,N-methyl-N-ethylsulfamoyl orN-methyl-N-(2-hydroxysulfonylethyl)sulfamoyl.

Z² may also be for example formylamino, acetylamino, propionylamino,butyrylamino or isobutyrylamino.

Z³ and Z⁴ may each also be for example methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl, methoxy, ethoxy, propoxy, isopropoxy,butoxy, isobutoxy, sec-butoxy, methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl or butylsulfonyl.

Fiber-reactive radicals E are those which react substitutively oradditively with the hydroxyl or nitrogen groups of the substrates to betreated.

Substitutively means, for example in the case of the reaction of thefiber-reactive radical with the hydroxyl groups of cellulose, that theleaving group or atoms (eg. fluorine or chlorine) in the fiber-reactiveradical E are replaced by the hydroxyl groups of cellulose in accordancewith the following scheme: ##STR5##

Additively means, for example in the case of a reaction of thefiber-reactive radical with the hydroxyl groups of cellulose, that thehydroxyl groups of cellulose add to the fiber-reactive radical inaccordance with the following scheme: ##STR6##

Heterocyclic fiber-reactive radicals E are for examplehalogen-substituted radicals of 1,3,5-triazine, quinoxaline,phthalazine, pyrimidine or pyridazone, or the2-alkylsulfonylbenzothiazole radical.

Examples are the following heterocyclic radicals: ##STR7## wherein Halis fluorine or chlorine,

U¹ is hydrogen or nitro, and

U² and U³ singly are independently of each other hydrogen or C₁ -C₆-alkyl, which may be substituted by hydroxyl, halogen, cyano,hydroxysulfonyl or a radical of the formula --SO₂ --Y, wherein Y is asdefined above, and may be interrupted by 1 or 2 oxygen atoms in etherfunction, by imino or by C₁ -C₄ -alkylimino groups, or together with thenitrogen atom joining them together pyrrolidinyl, piperidinyl,morpholinyl, piperazinyl or N-(C₁ -C₄ -alkyl)piperazinyl, or else U² isa radical of the formula ##STR8## where the rings F and K may each bemonosubstituted or disubstituted by hydroxysulfonyl and benzofused andthe ring K may independently thereof be monosubstituted or disubstitutedby chlorine, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, cyano, carboxyl,acetylalnino, hydroxysulfonylmethyl methyl or a radical of the formulaCH₂ --SO₂ --Y, SO₂ --Y, NH--CO--Y or NU² --CO--NU² --L¹ --SO₂ --Ywherein Y and U² are each as defined above and L¹ is C₂ -C₆ -alkylene,which may be substituted by hydroxyl, chlorine, cyano, carboxyl, C₁ -C₄-alkoxycarbonyl, C₁ -C₄ -alkanoyloxy or sulfato and may be interruptedby 1 or 2 oxygen atoms in ether function or by imino or C₁ -C₄-alkylimino groups.

Fiber-reactive radicals W of the aliphatic series are for exampleacryloyl, mono-, di- or trichloroacryloyl, --CO--CCl═CH--COOH,--CO--CH═CCl--COOH, 2 -chloropropionyl, 3-phenylsulfonylpropionyl,3-methylsulfonylpropionyl, 2-sulfatoethylaminosulfonyl,2-fluoro-2-chloro-3,3-di-fluorocyclobut-1-yl-carbonyl,2,2,3,3-tetrafluorocyclobut-1-yl-carbonyl,2,2,3,3-tetrafluorocyclobut-1-ylsulfonyl, 2-(2,2,3,3-tetrafluorocyclobut-1-yl) acryloyl, 1 - or 2-bromoacryloyl, 1-or 2-alkyl- or -aryl-sulfonylacryloyl, such as 1- or2-methylsulfonylacryloyl, 1,2-dichloropropionyl, 1,2-dibromopropionyl ora radical of the formula SO₂ --Y where Y is as defined above.

Suitable bridge members L which link the aliphatic fiber-reactiveradical W to the amino group of the formazan conform for example to theformula ##STR9## where U⁴ is hydrogen, C₁ -C₄ -alkyl, carboxyl, C₁ -C₄-alkoxy, halogen, nitro or hydroxysulfonyl,

is hydrogen, C₁ -C₆ -alkyl, which may be substituted by hydroxyl, C₁ -C₄-alkoxy, halogen, cyano, hydroxysulfonyl or a radical of the formula--SO₂ --Y, where Y is as defined above, or is substituted orunsubstituted phenyl, and L¹ is as defined above.

The fiber-reactive radical E may also comprise a further formazanradical which is either identical to the formazan radical alreadypresent or different therefrom.

Of particular suitability in this case are copper formazan dyes of theformula V ##STR10## where p is 0 or 1,

T is a radical of the formula ##STR11## where U⁶ is hydrogen or C₁ -C₄-alkyl and V² and V³ are each independently of the other hydrogen orhydroxysulfonyl, and L¹ is in each case as defined above, and

V¹ is hydrogen or the radical SO₂ --Y, and

Hal, X, Y, Z³ and Kat.sup.⊕ are each as defined above.

Preference is given to formazan dyes of the formula I where Me iscopper.

Preference is further given to formazan dyes of the formula I where mand n are each 1.

Preference is further given to formazan dyes of the formula I where Y isvinyl or a radical of the formula C₂ H₄ --Q where Q is chlorine, sulfatoor thiosulfato, in which chlorine is mentioned in particular.

Preference is further given to formazan dyes of the formula I where X isa radical of the formula CO--O.

Particular preference is given to formazan dyes conforming to theformula Ib ##STR12## where Z⁷ is hydrogen, C₁ -C₄ -alkyl,hydroxysulfonyl or halogen,

X¹ is a radical of the formula CO--O or SO₂ --O, and

Me, Y, E, Kat.sup.⊕ and the rings D and G are each as defined above.

Attention may be drawn in particular to formazan dyes of the formula Ic##STR13## where U², U³, Hal, X¹, Y, Z⁷ and Kat.sup.⊕ are each as definedabove.

Attention may further be drawn to formazan dyes of the formula Id##STR14## where L¹, X¹, Y, Z⁷ and Kat.sup.⊕ are each as defined above.

of particular interest are formazan dyes of the formula Ie ##STR15##where W¹ is a radical of the formula alk¹ --SO₂ --Y or where alk¹ is C₃-C₅ -alkylene, and

X¹, Y, Z⁷ and Kat.sup.⊕ are each as defined above.

Also of particular interest are formazan dyes of the formula If##STR16## where U⁷ is hydrogen or C₁ -C₄ -alkyl, which may besubstituted by a radical of the formula SO₂ -Y and may be interrupted byan oxygen atom in ether function,

L² is a radical of the formula ##STR17## -alk² - wherein U⁴ and U₆ areeach as defined above and alk² is in each case C₂ -C4-alkylene, whichmay be interrupted by an oxygen atom in ether function, and

X¹, Y, Z⁷ and Kat.sup.⊕ are each as defined above.

The present invention further relates to aminophenols of the formula II##STR18## where q is 0 or 2,

Y¹ is vinyl or a radical of the formula C₂ H₄ --Q¹, wherein Q¹ is agroup that is detachable under alkaline reaction conditions or hydroxyl,

L is C₂ -C₆ -alkylene, which may be substituted by hydroxyl, chlorine,cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkanoyloxy or sulfatoand may be interrupted by 1 or 2 oxygen atoms in ether function or byimino or C₁ -C₄ -alkylimino groups, U⁵ is hydrogen or C₁ -C₆ -alkyl,which may be substituted by hydroxyl, C₁ -C₄ -alkoxy, halogen, cyano,hydroxysulfonyl or a radical of the formula --SO₂ --Y¹, wherein Y¹ is asdefined above, or is substituted or unsubstituted phenyl, and

P is nitro or amino.

Preference is given to aminophenols of the formula IIa ##STR19## whereq, Y¹, L¹, U⁵ and P are each as defined above.

Especial mention must be given to aminophenols of the formula II whereL¹ is C₂ -C₄ -alkylene, which may be interrupted by one oxygen atom inether function.

Especial mention must further be given to aminophenols of the formula IIwhere U⁵ is hydrogen or C₁ -C₄ -alkyl, which may be substituted by aradical of the formula SO₂ ═--Y¹ and may be interrupted by an oxygenatom in ether function.

The novel aminophenols of the formula II are useful intermediates forpreparing the formazan dyes of the formula I.

We have further found that the aminophenols of the formula II areobtainable in an advantageous manner by reacting a benzoxazolone of theformula III ##STR20## where P is as defined above, with an amine of theformula IV ##STR21## where q, U⁵, L¹ and Y¹ are each as defined above.

The process of the invention is advantageously carried out in water orin a polar organic solvent, for example in a C₁ -C₄ -alkanol or inN,N-dimethylformamide, at from 50° to 95° C. and at a pH of from 5 to 9,preferably from 6 to 7.5.

Thereafter conventional methods can be employed, if necessary, tooxidize the thioether to a sulfone group, to reduce the nitro to anamino group, and to introduce the alkali-detachable group Q.

The benzoxazolones of the formula III can be obtained in a conventionalmanner, for example by reaction of the corresponding o-aminophenols withphosgene, as more particularly described in the Examples.

In a preferred embodiment of the process according to the presentinvention, the benzoxazolones formed in the reaction of the saido-aminophenols with phosgene can be used direct, i.e. without any needto isolate them first, in the novel preparation process.

The novel formazan dyes of the formula I can be obtained in aconventional manner. One possible option is to react a hydrazone of theformula VI ##STR22## where n, X, Y and the rings A and C are each asdefined above, with a diazonium salt derived from a formylaminophenol ofthe formula VII ##STR23## where the ring B is as defined above, in thepresence of a copper or nickel salt, eg. copper sulfate or nickelsulfate, and then hydrolyzing the product by the method described in theearlier European Patent Application 93 107 173.0. The hydrazones of theformula VI are known from the earlier European Patent Application P 4230 095.9. The preparation of the formylaminophenols VII is described inearlier European Patent Application 93 107 173.0.

The hydrolysis product is the dye of the formula VIII ##STR24## where n,Me, X, Y, Kat.sup.⊕ and the rings A, B and C are each as defined above,which can then be further reacted with a fiber-reactive component of theformula IX

    E--Lg                                                      (IX)

where Lg is a leaving group, eg. chlorine or bromine, and E is asdefined above.

In the preparation of those reactive dyes of the formula I which containa triazine ring, the fiber-reactive component IX is for example cyanuricchloride. In this case the reaction with the dye of the formula VIII isfollowed by reaction with the amine of formula X ##STR25## where U² andU³ are each as defined above. It is also possible first to condense thecyanuric chloride with the amine X and then to react the resultingtriazine derivative with the dye VIII.

However, it is also possible, in particular in the preparation of theformazan dyes of the formula Id, to employ the methods more particularlydescribed in U.S. Pat. No. 5,023,274 or U.S. Pat. No. 4,841,028, both ofwhich are hereby expressly incorporated herein by reference.

An advantageous method for preparing formazan dyes of the formula Iffurther comprises reacting hydrazones of the formula VI with a diazoniumsalt derived from an aminophenol of the formula XI ##STR26## where U⁷,L¹ and Y are each as defined above, in the presence of a copper ornickel salt, eg. copper sulfate or nickel sulfate.

The novel formazan dyes of the formula I are advantageously useful fordyeing or printing hydroxyl- or nitrogen-containing organic substrates.Examples of substrates of this type are leather and fiber materialspredominantly comprising natural or synthetic polyamides or natural orregenerated cellulose. The novel dyes are particularly advantageous fordyeing and printing textile material based on wool or in particularcotton. The dyeings obtained have reddish blue shades.

Cellulose-based substrates in particular are dyed in deep shades with avery high degree of fixation, the dyeings having a very goodlightfastness and excellent wetfastness properties, such as wash,chlorine bleach, peroxide bleach, alkali, seawater or perspirationfastness.

Embodiments of the invention will now be more particularly described byway of example.

EXAMPLE 1

34.8 g of 2-formylamino-6-aminophenol-4-sulfonic acid were dissolved in300 ml of water, cooled down to 0° to 5° C. and adjusted to pH 2 with 50ml of concentrated hydrochloric acid. Then the aminophenol wasdiazotized at 0°-5° C. with 40 g of 23% strength by weight aqueoussodium nitrite solution.

The resulting diazo suspension was added at 10°-15° C. to a pH 6.5-7.0mixture of 53.6 g of the hydrazone of the formula ##STR27## and 34.9 gof copper sulfate pentahydrate in 300 ml of water, the pH beingmaintained within the range from 6.5 to 7.0 by sprinkling with sodiumbicarbonate. After the addition had ended, the mixture was stirred at15°-20° C. for a further 12 hours.

It was then heated to 60° C., adjusted to pH 1 with concentratedhydrochloric acid and subsequently stirred at 60° C. for 3 hours.

Following complete hydrolysis (TLC) the pH was adjusted to 6.5 withsodium bicarbonate, and the precipitated product was filtered off anddried at 50° C. under reduced pressure.

The dried product obtained amounted to 95 g of an electrolyte-containingcopper formazan of the formula ##STR28##

The same method gives the formazans listed below in Table 1.

                                      TABLE 1                                     __________________________________________________________________________    Bsp. -Nr.Kupferformazan                                                       __________________________________________________________________________     ##STR29##                                                                     ##STR30##                                                                     ##STR31##                                                                     ##STR32##                                                                     ##STR33##                                                                    __________________________________________________________________________

EXAMPLE 7

a) 19 g of the copper formazan compound of the formula ##STR34## weredissolved in 200 ml of water. 0.6 g of disodium hydrogenphosphate wasadded, the mixture was cooled down to 0°-5° C. and a solution of 3.69 gof cyanuric chloride in 25 ml of acetone was added over 5 minutes. ThepH was maintained at 6.0-6.5 with 5% strength by weight aqueous sodiumbicarbonate solution, and the condensation was completed under the aboveconditions (TLC), which took about 1 hour.

b) Then a solution of 5 g of aniline-3-sulfonic acid in 200 ml of water,adjusted to pH 6, was added. The temperature was raised to 60° C and themixture was subsequently stirred at that temperature for one hour whilethe pH was maintained at from 6.0 to 6.5 with 5% strength by weightaqueous sodium bicarbonate solution.

The resulting reactive dye was salted out with 150 g of sodium chloride.The dye obtained has the formula ##STR35## and dyes cotton in a reddishblue shade having very good fastness properties.

EXAMPLE 8

Example 7 was repeated with 5.13 g of taurine instead of theaniline-3-sulfonic acid, affording, after salting out, a dye of theformula ##STR36## which dyes cotton in a reddish blue shade with verygood fastness properties.

EXAMPLE 9

9.33 g of 4-(2-sulfatoethyl)sulfonylaniline were dissolved in 200 ml ofwater at pH 6.5 and 0°-5° C. A suspension of 5.53 g of cyanuric chloridein 50 g of icewater was added and the mixture was subsequently stirredat 0°-5° C. and pH 6.5 for 2 hours.

The resulting suspension of the dichlorotriazine of the formula##STR37## was admixed at 10°-15° C. with a solution in 150 ml of waterof 15.7 g of the copper formazan described in Example 1.

The mixture was subsequently stirred at 10°-15° C. for 6 hours duringwhich the pH was maintained at 6.0 to 6.5 with 5% strength by weightaqueous sodium bicarbonate solution.

The resulting reactive dye was salted out with 300 g of sodium chloride.

The dye obtained has the formula ##STR38## and dyes cotton in a reddishblue shade having very good fastness properties.

The dyes listed below in Tables 2 and 3 can be obtained in a similarmanner.

                                      TABLE 2                                     __________________________________________________________________________     ##STR39##                                                                    Bsp.-                                                                            Position                                                                   Nr.                                                                              von SO.sub.3 H                                                                      R X Y                                                                __________________________________________________________________________    10 4     H Cl                                                                               ##STR40##                                                       11 4     H Cl                                                                               ##STR41##                                                       12 4     H Cl                                                                               ##STR42##                                                       13 4     H Cl                                                                               ##STR43##                                                       14 4     H Cl                                                                               ##STR44##                                                       15 4     H Cl                                                                               ##STR45##                                                       16 4     H Cl                                                                               ##STR46##                                                       17 4     H Cl                                                                               ##STR47##                                                       18 4     H Cl                                                                               ##STR48##                                                       19 4     H Cl                                                                               ##STR49##                                                       20 4     H Cl                                                                               ##STR50##                                                       21 4     H Cl                                                                               ##STR51##                                                       22 4     H Cl                                                                              NH.sub.2                                                         23 4     H Cl                                                                              NHCH.sub.3                                                       24 4     H Cl                                                                              NHCH.sub.2 CO.sub.2 H                                            25 4     H Cl                                                                              N(CH.sub.3).sub.2                                                26 4     H Cl                                                                               ##STR52##                                                       27 4     H Cl                                                                              NHC.sub.2 H.sub.4 OH                                             28 4     H Cl                                                                              NHC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 Cl                    29 4     H Cl                                                                              NHC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H           30 4     H Cl                                                                               ##STR53##                                                       31 4     H Cl                                                                              NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 CH CH.sub.2          32 4     H Cl                                                                               ##STR54##                                                       33 4     H Cl                                                                              NHC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 Cl                    34 4     H F                                                                                ##STR55##                                                       35 5     H Cl                                                                               ##STR56##                                                       36 5     H Cl                                                                               ##STR57##                                                       37 4     Cl                                                                              Cl                                                                               ##STR58##                                                       38 4     H F                                                                                ##STR59##                                                       39 4     Cl                                                                              Cl                                                                               ##STR60##                                                       40 4     H F                                                                                ##STR61##                                                       41 5     H F                                                                                ##STR62##                                                       42 5     H Cl                                                                               ##STR63##                                                       43 5     H F                                                                                ##STR64##                                                       44 4     Cl                                                                              Cl                                                                               ##STR65##                                                       45 4     H F                                                                                ##STR66##                                                       46 5     H Cl                                                                              NH.sub.2                                                         47 5     Cl                                                                              Cl                                                                              NHCH.sub.3                                                       48 5     H Cl                                                                              NHCH.sub.2 CO.sub.2 H                                            49 5     Cl                                                                              Cl                                                                              N(CH.sub.3).sub.2                                                50 4     Cl                                                                              Cl                                                                               ##STR67##                                                       51 4     Cl                                                                              F NHC.sub.2 H.sub.4 OH                                             52 4     Cl                                                                              F NHC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 Cl                    53 4     H F NHC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H           54 4     H F                                                                                ##STR68##                                                       55 5     H F NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2           56 5     H F                                                                                ##STR69##                                                       57 5     H F NHC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 Cl                    __________________________________________________________________________

                  TABLE 3                                                         ______________________________________                                         ##STR70##                                                                    Bsp.-                                                                              Position                                                                 Nr.  von SO.sub.3 H                                                                          X     Y                                                        ______________________________________                                        58   4         Cl                                                                                   ##STR71##                                               59   5         Cl                                                                                   ##STR72##                                               60   4         F                                                                                    ##STR73##                                               61   5         Cl                                                                                   ##STR74##                                               62   4         Cl    HNC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 Cl            63   4         F     HNC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 CHCH.sub.                         2                                                        ______________________________________                                    

EXAMPLE 64

Example 7b was repeated with 15.9 g of the dichlorotriazinyl copperformazan described in Example 7a instead of the aniline-3-sulfonic acid,affording, after salting out, a reactive dye of the formula ##STR75##which dyes cotton in a deep reddish blue shade having very good fastnessproperties.

EXAMPLE 65

38 g of the dichlorotriazine of the formula ##STR76## whose preparationis described in Example 1 of U.S. Pat. No. 5,004,807, were dissolved in500 ml of water at pH 6.5 and 20°-25° C. After 20.9 g of the copperformazan dye of

Example 1 had been added, the mixture was heated to 60° C. andsubsequently stirred at that temperature for 3 hours during which the pHwas maintained within the range from 6.0 to 6.5 with 5% strength byweight aqueous sodium bicarbonate solution. Cooling down to roomtemperature yielded the reactive dye of the formula ##STR77## which dyescotton in a reddish blue shade having very good fastness properties.

EXAMPLE 66

28.9 g of the copper formazan compound of the formula ##STR78## weredissolved in 400 ml of water. 0.6 g of disodium hydrogenphosphate wasadded, the mixture was cooled down to 0°-5° C., and a solution of 7.4 gof cyanuric chloride in 75 ml of acetone was added over 5 minutes. ThepH was maintained within the range from 6.0 to 6.5 with 5% strength byweight aqueous sodium bicarbonate solution, and the condensation wascompleted under the above conditions (TLC), which took about 1 hour.Then a solution of 5.46 g of 2-methylamino-4-aminobenzenesulfonic acidin 100 ml of water, adjusted to pH 6, was added. The temperature wasraised to 60° C. and the mixture was subsequently stirred at thattemperature for 2 hours. Isolation by salting out with 150 g of sodiumchloride yielded a dye of the formula ##STR79## which dyes cotton in areddish blue shade having very good fastness properties.

EXAMPLE 67

78.7 g of the aminophenol of the formula ##STR80## were dissolved in 600ml of water, cooled down to 0°-5° C. and brought to pH 2 withconcentrated hydrochloric acid. Then the aminophenol was diazotized at0°-5° C. with 51 g of 23% strength by weight aqueous sodium nitritesolution.

The resulting diazo suspension was added at 10°-15° C. to a mixture,adjusted to pH 6.5-7.0, of 75.8 g of hydrazone of the formula ##STR81##and 44.9 g of copper sulfate pentahydrate in 750 ml of water while thepH was maintained within the range from 6.5-7.0 by sprinkling withsodium bicarbonate. After the addition had ended, the mixture wasstirred at 15°-20° C. for 12 hours.

The precipitated dye was filtered off with suction and washed with 20%strength by weight aqueous sodium chloride solution.

The moist filter residue obtained, which gives a bluish green solutionin water and shows characteristic absorptions in the UV spectrum at 400run and 633 nm, was stirred up in 820 ml of water for the purpose ofconversion into the more stable complex. The pH was adjusted to 1 withconcentrated hydrochloric acid. The mixture was subsequently stirred atroom temperature for 12 hours.

Sodium carbonate was added to adjust the pH to 6.5-7.0. The resultingreactive dye was salted out with 150 g of sodium chloride. The dyeobtained has the formula ##STR82## and dyes cotton in a deep reddishblue shade having very good fastness properties.

EXAMPLE 68

72.6 g of the copper formazan described in Example 1 were dissolved in400 ml of water at pH 6 and cooled down to 0°-5° C. 26.5 g of theisocyanate of the formula

    OCN--C.sub.2 H.sub.4 --SO.sub.2 --C.sub.2 H.sub.4 Cl,

the preparation of which is described for example in Example 1 of U.S.Pat. No. 4,841,028, were added dropwise over 30 minutes during which thepH was maintained at from 6.0 to 6.2. After complete conversion (TLC),which took about 2 hours, the reactive dye formed was precipitated with150 g of sodium chloride.

The dye obtained has the formula ##STR83## and dyes cotton in a deepreddish blue shade having very good fastness properties.

EXAMPLE 69

72.6 g of the copper formazan described in Example 1 were dissolved in400 ml of water at pH 6.5 and cooled down to 5°-10° C. 26.8 g of theacid chloride of the formula

    ClCO--C.sub.3 H.sub.6 --SO.sub.2 --C.sub.2 H.sub.4 Cl,

were added dropwise at pH 6.0-6.5 and 10° C. The mixture wassubsequently stirred for 4 hours and then 100 g of sodium chloride wereadded. The precipitated dye was filtered off and dried at 40° C. underreduced pressure.

The reactive dye obtained has the formula ##STR84## and dyes cotton in adeep reddish blue shade having very good fastness properties.

The method of Examples 67, 68 and 69 also gives the reactive dyes listedbelow in Table 4. ##STR85##

                                      TABLE 4                                     __________________________________________________________________________    Ex.                                                                              Position                                                                   No.                                                                              of SO.sub.3 H                                                                      R Z                                                                   __________________________________________________________________________    70 5    H CONHC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H            71 4    Cl                                                                              CONHC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H            72 5    H CONHC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 Cl                     73 4    H CONHC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OCOCH.sub.3            74 5    H CONHC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OCOCH.sub.3            75 4    H CONHC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H            76 4    Cl                                                                              CONHC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H            77 5    H CONHC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H            78 4    H CONCH.sub.3 C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3                H                                                                   79 5    H CONCH.sub.3 C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3                H                                                                   80 4    H CONCH.sub.3 C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 Cl             81 4    H CON(C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H).sub.2               .                                                                   82 5    H CON(C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H).sub.2     83 4    Cl                                                                              CON(C.sub.2 H.sub.4SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H).sub.2      84 4    H CONHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4                 OSO.sub.3 H                                                         85 5    H CONHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4                 OSO.sub.3 H                                                         86 4    Cl                                                                              CONHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4                 OSO.sub.3 H                                                         87 4    H CON(C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 Cl).sub.2              88 5    H CON(C.sub. 2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 Cl).sub.2             89 4    H                                                                     90 4    H                                                                                ##STR86##                                                          91 4    H                                                                                ##STR87##                                                          92 5    H COC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 Cl                       93 4    Cl                                                                              COC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 Cl                       94 4    H                                                                                ##STR88##                                                          95 5    H                                                                                ##STR89##                                                          96 4    H                                                                                ##STR90##                                                          97 4    Cl                                                                               ##STR91##                                                          98 4    H                                                                                ##STR92##                                                          99 5    H                                                                                ##STR93##                                                          100                                                                              4    H                                                                                ##STR94##                                                          101                                                                              5    H                                                                                ##STR95##                                                          102                                                                              4    H                                                                                ##STR96##                                                          __________________________________________________________________________

EXAMPLE 103

a) To 160 g of sodium hydroxide in 1.5 l of water 232 g of3-amino-4-hydroxy-5-nitrobenzenesulfonic acid were added with cooling at20°-40° C. The reaction mixture was cooled down to 0°-5° C., and then182 g of phosgene were introduced over 8 hours while the pH wasmaintained at ≦10 with 150 g of 50% strength by weight sodium hydroxidesolution. The mixture was subsequently stirred for one hour, and excessphosgene was then expelled with nitrogen. The pH was adjusted to 7 with200 g of concentrated hydrochloric acid. To the resulting7-nitrobenzoxazol-2-one-5-sulfonic acid (sodium salt) were added 133 gof 2'-aminoethyl 2-hydroxyethyl sulfide and the pH was adjusted to 7with 164 g of concentrated hydrochloric acid. The mixture was heated to60° C. and stirred at that temperature for 6.5 hours. After completeconversion (TLC), it was adjusted to pH 5 with concentrated hydrochloricacid, and 0.50 g of tungstic acid were added, followed over 2 hours bythe dropwise addition of 340 g of 30% strength by weight hydrogenperoxide. The mixture was subsequently stirred at 60° C. for a further 2hours until conversion was complete (TLC). After cooling down to 0°-5°C. the mixture was adjusted to pH 0.5-1.0 with 150 g of concentratedhydrochloric acid, and the precipitated product was filtered off withsuction. Drying at 70°-80° C. under reduced pressure yielded 377 g of acompound of the formula ##STR97##

¹ H-NMR [D⁶ -DMSO]: δ=3.3 (CH₂), 3.4 (CH₂), 3.6 (CH₂), 3.8 (CH₂), 5.2(OH), 7.3 (NH), 7.7, 8.6 (aromatics H), 11.0 (NH) ppm

b) 306 g of the nitro compound obtained under a) were dissolved in 3 lof water. 5 g of palladium catalyst (10% strength on carbon) were added,and a hydrogenation was carried out at 35°-40° C. After the uptake ofhydrogen had ceased, the catalyst was filtered off and the mother liquorwas evaporated to dryness, leaving 280 g of the compound of the formula##STR98##

¹ H-NMR [D⁶ -DMSO]: δ=3.30, 3.35, 3.55, 3.80 (in each case CH₂), 4.00(OH), 7.10 (NH), 7.35, 7.50 (aromatics H), 9.20 (OH) 11.5 (NH)

EXAMPLE 104

280 g of the aminophenol obtained in Example 103b were added withice-cooling at 10°-15° C. to 1120 g of chlorosulfonic acid and themixture was subsequently stirred at room temperature for about 12 hours.After conversion was complete (TLC), the mixture was poured onto 4 l ofice, and the precipitated product was filtered off with suction andwashed neutral with water. Drying under reduced pressure at 30°-40° C.left 302 g of the compound of the formula ##STR99## which can be usedwithout further purification for dye syntheses as described for examplein Example 67.

EXAMPLE 105

a) Example 103a was repeated, except that the3-amino-4-hydroxy-5-nitrobenzenesulfonic acid was replaced by 232 g ofthe isomeric 2-hydroxy-3-amino-5-nitrobenzenesulfonic acid affording,after drying at 70°-80° C. under reduced pressure, 365 g of a compoundof the formula ##STR100##

b) The nitro compound described under a) was reduced according toExample 103b and 280 g of the resulting amino compound were esterifiedwith chlorosulfonic acid according to Example 104, affording, afterdrying at 30°-40° C. 295 g of the compound of the formula ##STR101##

The method of Example 103 or 104 also gives the aminophenols listedbelow in Table 5.

    ______________________________________                                         ##STR102##                                                                   Example                                                                       No.    R      Z                                                               ______________________________________                                        106    NO.sub.2                                                                             NHC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OH                   107    NH.sub.2                                                                             NHC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OH                   108    NH.sub.2                                                                             NHC.sub.3 H.sub.6 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3 H          109    NO.sub.2                                                                             N(CH.sub.3)C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH          110    NH.sub.2                                                                             N(CH.sub.3)C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH          111    NH.sub.2                                                                             N(CH.sub.3)C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4                           OSO.sub.3 H                                                     112    NO.sub.2                                                                             NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4                   OH                                                              113    NH.sub.2                                                                             NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4                   OH                                                              114    NH.sub.2                                                                             NHC.sub.2 H.sub.4 OC.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4                   OSO.sub.3 H                                                     115    NO.sub.2                                                                              ##STR103##                                                     116    NH.sub.2                                                                              ##STR104##                                                     117    NH.sub.2                                                                              ##STR105##                                                     118    NO.sub.2                                                                             N(C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH).sub.2            119    NH.sub.2                                                                             N(C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OH).sub.2            120    NH.sub.2                                                                             N(C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4 OSO.sub.3                          H).sub.2                                                        121    NO.sub.2                                                                              ##STR106##                                                     122    NH.sub.2                                                                              ##STR107##                                                     123    NH.sub.2                                                                              ##STR108##                                                     124    NO.sub.2                                                                              ##STR109##                                                     125    NH.sub.2                                                                              ##STR110##                                                     126    NH.sub.2                                                                              ##STR111##                                                     ______________________________________                                    

We claim:
 1. An Aminophenol of the formula II ##STR112## where q is 0 or2,Y¹ is vinyl or a radical of the formula C₂ H₄ --Q¹, wherein Q¹ is agroup that is detachable under alkaline reaction conditions or hydroxyl,L¹ is C₂ -C₆ -alkylene, which may be substituted by hydroxyl, chlorine,cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkanoyloxy or sulfatoand may be interrupted by 1 or 2 oxygen atoms in ether function or byimino or C₁ -C₄ -alkylimino groups, U⁵ is hydrogen or C₁ -C₆ -alkyl,which may be substituted by hydroxyl, C₁ -C₄ -alkoxy, halogen, cyano,hydroxysulfonyl or a radical of the formula --SO₂ --Y¹, wherein Y¹ is asdefined above, or is substituted or unsubstituted phenyl, and P is nitroor amino.